Monoazo dyestuffs containing a 6-hydroxynaphthostyrile group



3,462,403 MUNOAZO DYESTUFFS CONTAINING A 6-HY- DRQXYNAPHTHGSTYRILE GROUP Albrecht Hofimann, Cologne-Stammheim, and Gerhard Wolfram, ()pladen, Germany, assignors to Farbenfabriken Bayer Alttiengesellscllaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Jan. 17, 1966, Ser. No. 520,843 Claims priority, application Germany, Feb. 5, 1965,

int. or. can) 45736; 45/20, 29/36 US. Cl. 260-446 15 Claims ABSCT GF THE DISCLOSURE It has been found that valuable new dyestuffs of the general formula HO X 1|\N=N Ril lo=o (I) wherein A denotes the radical of a diazo component, in which X is in the o-position to the azo group, X is a group forming metal complexes or a substituent which is convertible into such a group under the conditions of metallisation, R denotes hydrogen or a lower alkyl group which may be further substituted, R represents hydrogen or a substituent, and n stands for the number 1 or 2,

or their metal compounds, are obtained, when a diazo compound containing in the o-position to the diazo group a group capable of forming metal complexes or a substituent convertible into such a group under the conditions of rnetallisation, is coupled with a coupling component of the structure in which R R and n have the stated meaning, and the resultant azo dyestuffs are optionally treatd in substance or on the fibre with metal-yielding agents, optionally in the presence of other azo or azomethine dyestuffs forming metal complexes.

Coupling of the starting components to produce the azo dyestufis (I) is carried out by known methods in the 3,462,4fl8 Patented Aug. 19, 1969 acidic, neutral or alkaline range in an aqueous, aqueousorganic or organi medium.

The following carhoand hetero-aromatic amines can be used as diazo components, for example:

Z-aminophenol, 4-chloro-2-aminopheno1, 4,S-dichloro-Z-aminophenol, 3,4,6-trichloro-2-aminophenol, 4-nitro-2-aminopheno1, 5-nitro-2-aminophenol, 4,6-dinitro-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-chloro-6-nitro-2-aminopher1ol, 6-chloro-4-nitro-2-aminophenol, 6-nitr0-2-amino-4-acetylamin0phen01, 3-amino-4-hydroxy-toluene, S-nitro-3-amino-4-hydroxy-toluene, Z-aminophenol-4-sulphonic acid, 2-aminophenolksulphonic acid amide, Z-aminophenol-4-sulphonic acid methylarnide, 2-aminophenol-4-sulphonic acid-dirnethyl amide, 2-aminophenol-4-sulphonic acid-,B-hydroxy-ethylamide, 2-aminophenol-4-sulphonic acid-morpholide, 6-chloro-Z-aminophenol-4-sulphonic acid, 5-nitro-2-aminophenol-4-sulphonic acid, 6-nitro-2-aminophenol-4-sulphonic acid, 2-aminophenol-S-Sulphonic acid, Z-aminophenol-5-sulphonic acid amide, Z-aminophenol-S-sulphonic acid dimethylamide, 2-aminophenol-5-sulphonic acid morpholide, 4-chloro-2-aniinophenol-5-sulphonic acid, 4-chl0ro-2-aminophenol-6-sulphonic acid, 4-nitro-2-aminophenol-6-sulphonic acid, 2-amino-4-acetaminophenol--sulphonic acid, 2-aminophenol-4-6-disulphonic acid, 3-amino-2-hydroxy-benzoic acid, 5-nitro-3-amino-2-hydroxy-benzoic acid, 3-amino-4-hydroxy-benzoic acid, 3-amino-2-hydroxy-5-methyl-benzoic acid, 3-amino-2-hydroxy-l-benzoic acid-S-sulphonic acid, (3-amino4-hydroxy-phenyl) -ethyl-sulphone, 3-amino-4-hydroxydiphenylsulphone, 3-amino-4-hydroxy-benzene-methylenesulphone-(2)- ether- 1), l-amino-Z-napthol, 2-amino-3-naphthol, l-amino-naphthol- (2 -sulphonic acid- 6 2-amino-naphthol-( l -sulphonic acid-(4), Z-amino-n aphthol- 3 -sulphonic acid-( 6 2-amino-3-naphthol-disulphonic acid-(6,8), Z-amino-benzoic acid, 4-chloro-2-amino-benzoic acid, 5-chloro-2-amino-benzoic acid, 6-chloro-2-amino-benzoic acid, 4-nitro-2-arnino-benz0ic acid, S-nitro-Z-amino-benzoic acid, 4-acetylamino-2-amino-benzoic acid, 5-acetylamino-2-amino-benzoic acid, 3-5-dichloro-amino-benzoic acid, Z-aminobenzoic acid-(1)-sulphonic acid-(4) Z-aminO-benzoic acid-(1)-sulphonic acid- (5 2-amino-benzoic acid-(1)-sulphonic acid-(4)-amide, 2-amino-naphthalene-3-carboxylic acid, Z-amino-naphthalene-3-carboxylic acid-o-sulphonic acid, 1-amin0-anthraquinone-2-carboxylic acid,

8-amino-quinoline,

Z-amino-pyridine,

Z-amino-benzthiazole, 6-methoXy-2-aminobenzthiazole, 6-ethoxy-2-amino-benzthiazole, 3-phenyl-5-amino-thiadiazole-( 1,2,4), 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid.

Suitable diazo components with an o-positioned alkoxy group are, for example:

2-amino-anisole,

4-ch1oro-2-amino-anisole, S-chloro-Z-amino-anisole, 4,5-dichloro-2-amino-anisole, 4-nitro-2-amino-anisole, 5-nitro-2-amino-anisole, 4-chloro-5-nitro-2-amino-anisole, 2-amino-4-acetamin0-anisole, 3-amino-4-methoxy-toluene, 3-amino-4-methoxy-6-benzoyl-amino-toluene, 6-chloro-3-amino-4-methoxy-toluene, 4-arnino-1,3-dimethoxybenzene, 6-chloro-4-amino-1,B-dimethoxybenzene, 2-arnino-1,4-dimethoxybenzene, S-amino-Z-acetamino-1,4-dimethoxybenzene, S-amino-Z-benzoylamino-1,4-dimethoxybenzene, Z-aminoanisle-4-sulphonic acid methylamide, 2-amino-anisole-4-sulphonic acid-diethylamide, 2-amino-anisole-4-sulphonic acid-n-butylamide, 2-amino-anisole-4-sulphonic acid-di-n-butylamide, 2-aminoanisole-4-sulphonic acid-morpholide, S-nitro-Z-amino-anisole-4-sulphonic acid, 2-amino-1,4-dimethoxybenzene-S-sulphonic acid amide, 3-amino-4-methoxybenzoic acid, 4-amino-3-methoxy-diphenyl-amine,

( 3-amino-4-methoxy-phenyl) -ethyl-sulphone, 3-amino-4-methoxy-diphenylsulphone,

(3 -amino-4-methoxy-phenyl -benzylsulphone, 2-amino-3-meth0xy-diphenylene-oxide.

Suitable diazo components are also amines carrying in the o-position to the amino group a halogen atom, a sulpho group or a hydrogen atom which are converted by the metallisation into metal complex-linked hydroxyl groups, such as 2-chloroaniline,

2,3-dichloroaniline,

2,4-dichloroaniline,

2,5-dichloroaniline,

2-chloro-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 4-chloro-3-amino-toluene, 4,6-dichloro-3-amino-toluene, 4-chloro-3-amin0benzene-l-sulphonic acid, 3-chloro-4-amino-benzene-l-sulphonic acid, 2,5-dichloro-4-aminobenzene-l-sulphonic acid, 4-chloro-6-nitro-3-amino-anisole, 4-chloro-3-amino-benzoic acid, 1-chloro-2-amino-anthraquinone; 2-amino-benzene-l-sulphonic acid, 4-chloroaniline-Z-sulphonic acid, S-chloroaniline-Z-sulphonic acid, 4,S-dichloroaniline-Z-sulphonic acid, 4-nitro-aniline-2-sulphonic acid, 4-amino-toluene-3-sulphonic acid, Z-aminobenzene-disulphonic acid-( 1,4), 4-arninobenzene-disulphonic acid-( 1,3

4- (N-acetylamino -2-aminobenzene-sulphonic acid-( 1), 5- (N-acetylarnino -2-aminobenzene-sulphonic acid-(1), 4-amino-anisole-sulphonic acid- 3 naphthylamine-( l -sulphonic acid- (2) naphthylamine-(2)-sulphonic acid-(1), naphthylamine- (2 -disulphonic acid- (3 ,6), naphthylamine- 2) -disulphonic acid- (3 ,7) 3-chloroaniline,

4-chloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 3-nitroaniline,

4-nitroaniline,

3-aminotoluene, 6-chloro-3-amino-toluene, 4-aminotoluene, 1-aminobenzene-3-sulphonic acid, 1-aminobenzene-4-sulphonic acid, l-naphthylamine, Z-naphthylamine, 1-naphthylamine-4-sulphonic acid, Z-naphthylamine-6-sulphonic acid and the like.

The 6-hydroxy-naphthostyriles used as coupling components can be prepared by methods known in principle and described, for example, in German patent specifications Nos. 645,241 and 679,977, in that naphthostyriles are nitrated, the nitro compound is reduced to the amino compound and the amino compound converted into the hydroxy compound by heating with sulphuric acid under pressure, or in that derivatives of S-hydroxynaphthalenel-carboxylic acid are coupled in the 8-position with a suitable diazonium compound, the dyestuffs reductively split and the resultant S-hydroxy-S-amino-naphthalene-1- carboxylic acid is cyclised to produce the corresponding 6-hydroxy-naphthostyrile.

Suitable coupling components are, for example:

6-hydroxy-naphthostyrile, 3-methyl-6-hydroxy-naphthostyrile, 5-methyl-6-hydroxy-naphthostyrile, S-ethyl-6-hydroxy-naphthostyrile, 3-chloro-6-hydroxy-naphthostyrile, 5-chloro-6-hydroxy-naphthostyrile, 3,5-dichloro-6-hydroxy-naphthostyrile, 3-methoxy-6-hydroxy-naphthostyrile, 5-methoxy-6-hydroxynaphthostyrile, 3-ethoxy-6-hydroxy-naphthostyrile, 4-nit1'o-6-hydr0xy-naphthostyrile, 3-acetylarnino-6-hydroxy-naphthostyrile, 5-acetylamino-6-hydroxy-naphthostyrile, 6-hydroxy-naphthostyrile-S-sulphonic acid, 6-hydroxy-naphth0styri1e-5-sulphonic acid amide, 6-hydroxy-naphthostyrile-S-sulphonic acid methylamide, 6-hydroxy-naphthostyrile-S-sulphonic acid dimethylamide, 6-hydroxy-naphthostyrile-5-methylsu1phone as well as the l-N-methyl, l-N-ethyl, l-N-butyl, 1-N- hydroxy, 1 N chloroethyl, l-N-acetoxyethyl, 1-N-/3- cyanoethyl and l-N-B-carbethoxyethyl derivatives of the stated compounds.

The naphthalene nucleus of the naphthostyrile coupling component, by definition, may contain one or two substituents. Examples are halogen substituents, especially chlorine, bromine or fluorine; alkyl, especially straight chain or branched lower alkyl groups, such as those with 1 to 5 carbon atoms; alkoxy, especially lower alkoxy radicals with 1 to 5 carbon atoms in the alkyl radical; acylamino groups, especially those which are derived from aliphatic or aromatic carboxylic acids or sulphonic acids, such as acetylamino, chloroacetylamino, cyanoacetylamino, hydroxacetylamino, alkoxyacetylamino, propionylamino, butyrylamino groups and the corresponding substitution products, benzoylamino radicals including those further substituted in the benzene ring of the benzoylamino group, benzene-sulphonylamino groups including those further substituted in the benzene ring, methylsulphonylamino, ethyl sulphonylamino, propionyl sulphonylamino groups, halotriazinylamino radicals such as monochloro-monoamino groups and substituted amino triazinylamino and dichloro-triazinylamino groups, halopyrimidinylamino groups, such as triand dichloropyrimidinylamino groups, 2,3-dihaloquinoxaline-6-carbonylor -sulphonylamino groups, 1,4-dihalophthalazine- 6-carbonylor -sulphonylamino groups, 2-haloor 2- methyl-sulphonyl-benzthiazole-S-carbonylor -sulphonylamino groups, fl-haloacetylamino, fl-halopropionylamino, haloacryloylamino and acryloylamino groups, halogen in the above substituents preferably standing for C1, but also for Br, nitro, sulphonic acid, carboxylic acid, sulphonamide, substituted sulphonamide groups, whereby the substituents can be alkyl, aralkyl, aryl radicals and substitution products of these radicals, alkyland aryl-sulphone groups, cyano, trifluoromethyl and disulphimide groups.

The aforesaid substituents are also especially suitable substituents for the radical A of the diazo component, which is preferably a radical of the benzene, naphthalene or heterocyclic series. Among the alkyl-sulphonyl and aryl-sulphonyl groups, the methyl-sulphonyl, ethyl-sulphonyl and phenyl-sulphonyl groups are of special interest, while among the sulphonamide groups the following substitution products may be mentioned as especially suitable, besides the unsubstituted sulphonamide group:

the monomethyl-sulphonamide, monoethyl-sulphonamide, monohydroxyl-sulphonarnide, monochloroethyl-sulphonamide, N-methyl-N-ethylsulphonamide, N,N-dimethyl-sulphonamide, N,N-diethyl-sulphonamide, N,N-dihydroxyl-sulphonamide, N,N-dipropyl-sulphonamide, sulphomorpholide, sulphopiperidide, N-phenyl-sulphonamide and the sulphonamide groups further substituted in the phenyl nucleus of the phenyl-sulphonamide group, e.g. by chloro, methyl, carboxy, nitro groups, or other sulphonamide groups which are further substituted. The radical of the diazo component can moreover contain further azo groups.

The optionally further substituted lower alkyl group R can be, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, [i-hydroxyethyl, fl-choroethyl, B-cyanoethyl ,B-acetoxyethyl, ,B-carbethoxyethyl, fl -carboxethyl group or an ethyl, propyl or butyl group substituted in a different way. Those lower alkyl groups are preferred, which contain a total number of 1 to 6 carbon atoms.

The conversion of the azo dyestuffs into their metal complex compounds is preferably carried out with compounds of chromium and cobalt. The metallisation is preferably performed in an aqueous solution or in an organic medium, e.g. in formamide, ethylene glycol, glycol monomethyl ether, in a urea melt or in a concentrated aqueous solution of an alkali metal salt of a low molecular aliphatic monocarboxylic acid; it is advantageous to use at least the amount of metal-yielding agent containing 1 metal atom per 2 monoazo dyestuff molecules.

Suitable chromium compounds are chromic fluoride, chromic chloride, chromic sulphate, chromic formate, chromic acetate, chromic potassium sulphate, chromic ammonium sulphate. Compounds of hexavalent chromium, such as sodium or potassium chromate or dichromate, are also suitable, if the process is carried out in a strongly alkaline medium in the presence of reducing agents, such as glucose.

Suitable cobalt compounds are cobaltous formate, cobaltous acetate or cobaltous sulphate, which may previously be converted into complexes of trivalent cobalt, for example by oxidation with hydrogen peroxide in an ammoniacal solution. If the metallisation is carried out in a concentrated aqueous solution of an alkali metal salt of a low molecular aliphatic carboxylic acid, water-insoluble metal compounds such as cobalt hydroxide or cobalt carbonate, can also be used. The metallisation is carried out with particular advantage in an aqueous-alkaline medium, the metal compounds being added in the presence of compounds which keep the metal dissolved in a complex linkage in a strongly alkaline medium, such as tartaric acid, citric acid or lactic acid. Other suitable metallising agents are e.g. copper salts, such as copper sulphate, iron salts, such as iron sulphate, or nickel salts, such as nickel sulphate.

If for the preparation of the dyestuffs according to the invention those diazo components are used, which carry a methoxy group in the o-position to the amino groups, then the monazo dyestuffs so obtained can also be converted into the metal complexes. The demethylating metallisation is preferably carried out in an aqueous or organic medium, for example, in ethylene glycol, glycol monomethyl ether or formamide, in the presence of basic compounds, such as e.g. ammonia, organic amines or alkalies. In this case, chromium compounds, such as chromic fluoride, chromic chloride, chromic sulphate etc., and copper compounds, such as copper chloride, copper sulphate and copper acetate, serve as metal-yielding agents. It is advantageous to add to the metallising mixture compounds which keep the metal dissolved in complex linkage in an alkaline medium, such as ammonia, glycerol, tartaric acid and nvridine.

Monoazo dyestuffs which are prepared by means of diazo components carrying a sulpho group in the o-position to the amino group, can also be converted into the metal complexes of the corresponding o,o-dihydroxy-azo dyestuffs, by treatment with metal-yielding, preferably copper-yielding, agents in an alkaline medium.

Those dyestuffs of the general Formula 1 in which X stands for a hydrogen atom, can be converted into the metal complexes of the corresponding o,o'-dihydroxy-azo dyestuffs by treatment with metal-yielding, preferably copper-yielding, agents in the presence of oxidising substances, such as oxygen, hydrogen peroxide and per-compounds.

The metal-free o,o'-dihydroxy-azo dyestuffs of the general Formula 1 can be prepared from their copper complexes by treatment with mineral acids and, if desired, transformed into other metal complexes, prefer-ably chromium or cobalt complexes, according to the stated processes.

To prepare pure asymmetrical 2:1 chromium complex dyestuffs it is advantageous to react the 1:1 chromium complex compound of a dyestuff of the Formula 1, in which X is OH or COOH with another metal-free dyestuff of the Formula 1 or with any other azo dyestuff forming metal complexes according to known methods to form the asymmetrical 2:1 chromium complex compound, or to react a metal-free dyestuff of the Formula 1 in which X denotes OH or COOH with the 1:1 chromium complex compound of any other azo dyestuff to form the 2:1 chromium complex compound.

In the range of the new dyestuffs (1) the metal complex compounds, and among these especially the chromium, cobalt and copper complexes, are particularly valuable in respect to their dyeing properties.

The isolation of water-insoluble metal complex dyestuffs of the type according to the invention is carried out by filtration after pouring the metallising solution into water. Water-soluble dyestuffs are previously separated from the solution by the addition of salts, such as sodium chloride, Glaubers salt or ammonium sulphate.

The new metal-free dyestuffs (1) are suitable for the dyeing of various fibre materials, for example, for the dyeing and printing of meta1-modified polypropylene fibres. In the form of their 2:1 chromium or cobalt complex compounds the new dyestuffs are eminently suitable for the dyeing of natural and synthetic polypeptide fibres, such as wool, silk, synthetic superpolyamides and polyurethanes. The water-soluble metal complex compounds are chiefly suitable for dyeing wool. Satisfactory results analogous manner, which yield dyeings in the stated shades when after-chromed on wool.

Diazo component 2-aminophenol-4-su1phonic acid amide 6chloro-2-aminophenol-4-sulphonic acid 5-nitro-2-aminopheno1-4-sulphonic acid. 6-nitro-2-aminophenol-4-sulphonic acid- 6 2 aminophenol-5-su'lphonie acid 7 Z-aminophenohdsulphonic acid amide" 4chioro-zaminophenol-fi-sulph0111c acid 4-nitro2-aminop enol-fi-suiphonic acid- 2-aminophenol-4-S11lphonic acid Z-aminophenol--sulphonic acid amide. 6-chl0ro-2-aminophenoli-sulphonic acid 5-I1itro-2ami11opheno1-4-sulphonlc acid.

2-aminophenol-5-sulphonic acid 2-aminophenol-fisulphonic acid amide 4-chloroQ-aminophenol-o-sulphonic acid 2-aminophenol-4-sulphonic acid 2-aminophenoli-sulphonic acid amide- 6 ch1oro-2-amin0phen0l4sulphonic acid 2-aminophenol-5-sulphonic acid 4 chloro-2-aminoghenol-G-suiphonic acid- 4-chloro-2-aminophenol-dsulphonic acid 4-nitro-2-aminophauol-B-sulphonic acid- 2-amiu0-4-acctamlnophenol-fi-sulphonic acid" 1-amino-6-nitro-2-naphthol-4-sulphonic acid--.

2-amino-4-acetaminophenol-S-sulphonic acid. 2-aminophcnol-4, odisulphonic acid 1-amino-6-nitro-2-naphthol-4-sulphonic acid.

TABLE 1 Shade after- Coupling component chromed on wool 6-hydroxy-naphthostyri1e Olive.

do Yellowish-olive.

e. Olive-green.

Yellowish brown.

Olive.

Greenish olive.

Reddish grey.

live.

Grey.

Olive.

Do. Yellowish olive. Olive.

5-nitro-2-an1inophen0l-4-sulphonic acid do G-nitro-2aminopheno1-4-sulphonic acid Olive-green. Yellowish brown.

Olive.

o. Greenish olive. Reddish grey.

Do. Yellowish olive.

Olive-green. Yellowish brown.

2-aminopheno1-5-sulphonic acid amide do.. 0. 4-cl1loro-2-aminophenol-5-sulphonic acid do Olive. 4-chloro 2-aminophenol-6-sulphonic acid -.do.. Do. 4-nitro-2-aminophenoi-G-sulphonic acid ..do.. Greenish olive. Z-amin0+acetaminophenol-B-sulphonic acid .do Rcddish grey. 2-aminophenol-4, 6-disulphonic acid .d0.- Olive. 38 1-amino-6-nltro-2rnaphthol4su1phonic acid .-do Grey.

then treated on the fibre with chromium-yielding agents.

Those new heavy metal complex dyestufis which are hardly soluble to insoluble in water prove to be especially valuable. They yield dyeings of very good fastness to light and wet processing on synthetic superpolyamide and polyurethane fibres.

In the following examples which are given for the pur pose of illustrating the invention, the parts are parts by weight. The temperatures are given in degrees centigrade.

Example 1 and dyes wool by the after-chroming method in olive shades of very good fastness to light and wet processing.

The following Table 1 gives further diazo and coupling components from which new dyestuffs are obtained in an Example 39 8.9 parts 4-chloro-2-aminophenol are dissolved in 50 parts water and 20 parts concentrated hydrochloric acid and the solution is diazotised at 0 with a solution of 4 parts sodium nitrite in 20 parts water. This mixture is added to a solution containing 12.4 parts l-N-ethyl-G- hydroxynaphthostyrile, 2.4 parts sodium hydroxide and 1 0 parts sodium carbonate in 100 parts water, stirred at 510 for 5 hours, the dyestutf is filtered off with suction, washed with water and dried at 8.5 parts of the dyestufi thus prepared are heated in parts formamide with 3.1 parts chromic chloride hexahydrate and 5.7 parts sodium acetate at for 4 hours. This mixture is subsequently added to 500 parts of a 2.5% sodium chloride solution at 50, allowed to cool down While stirring, the chromium complex is filtered off with suction, washed with water and dried at 90.

The 2:1 chromium complex dyestutf so obtained corresponds to the formula CQH5 N and dyes synthetic superpolyamide fibers in grey shades fast to light and washing.

With the diazo and coupling components listed in the following Table 2 there are obtained further dyestuffs which are converted into their 2:1 chromium complexes in a manner analogous to that described in Example 39. The chromium complexes dye synthetic superpolyamide fibres from a dispersion in the shades stated in the table.

TABLE 2 Example Shade on poly- N umber Dlazo component Coupling component amide fibres 40.-. Z-aminophenol 6-hydroxy-naphthostyrlle. Black. 41-. 4-chloro-2-amlnophenol ..d Blue-black. 42. 4,6-dicl1l0ro-2-aminopl\ennl .do Black 43.. 4nitro'2-aminophenol- ..do.. Olive. 44.. 5-nitro-2aminophenol do Do. 45.- 4-chloro-5-nitro-2-aminophenoldo Do. 46.. 4-chloro-6-nitro-2-aminophenol. ..do Do. 47.... G-chlom4 nitro-2-aminophenol. .do Olivegreen. 48.- 3-amino-4-hydroxytoluene d0.. live. 49.- 2-aminophenol-4-sulphonic acid dimethylami ..do.. Do. 50.- 2-aminophenol-5-sulphonic acid dimethylamide. ..d0.. Grey. 51.- 3-amino-4-hydroxyphenylJ-ethylsulph one... .do.. Black. 52.- 3-amino-d-hydroxy-diphenyl sulphone. .do D o. 53.- Z-aminophenol 1-N-methyl-fi-hydroxy-naphthos y11 e- Grey. 54.- 4-chloro2-aminophen0l .do Do. 55-- 4,6-dichloro-Z-aminophenol. do.. Black. 56-. 4-nitro-2-aminophenol ..do. Olive. 57.. fi-nitro-zaminophenol .do. Do. 58.- 4-chloro-5-nitro-2-aminophenol. .do-. Do. 59.- 4-cl1]oro-6-nitro-2-aminophenol ..do.. Do. 60.. 6-chloro-4-nitro-2-aminophenol. .d0.. olivegreen. 61 3-amino-4-hydroxy-toluene ..do.. Greenish olive. 62 Q-aminophenol-4-sulphonic acid dimethylamide. do.. Currant blue. 63-. Z-aminophenol-5-sulphonic acid dimethylamide. do-- Grey. 64.- 3-amino-4-hydroxyphenyl-l-ethylsulphone..- do.. Do. 65.- 3-amino4-hydroxy-diphenyl sulphone. 0 D0. 66.- Z-annnophenol l-N-ethyl-6-hydroxy-naphthostyri1e. Do. 67.- 4,6-dichloro-2-aminophenol -do D 68.- 4-nitro-2-aminophenoldo Olive. 69.- 5-nitro-2-aminophenol .do.. Do. 70.- 4-ehloro-5-nitro-2-amin0pheno do Do. 71.- 4chloro-6-nitr0-2-aminophenol. de Brown. 72.. 6-chloro4-nitro-2-aminophenol .do.. Olive-green. 73-. 3-amino4-hydroxytoluene .do.. live. 74.- 2-aminophenol-4-sulphonie acid dimethylamide. do-- Currant blue. 75.- Z-aminophenol-dsulphonic acid dimethylamidede Grey. 76.. 3-amino4-hydroxyphenyl-l-ethylsulphone.. do.. Do. 77 3-amino-4-hydroxy-diphenylsulphone -.d0 D0.

Example 78 11.7 parts 3-amino-4-hydroxyphenyl 1 ethyl-sulphone are dissolved in 100 parts water and parts concentrated hydrochloric acid and the solution is diazotised at 0 with a solution of 4 parts sodium nitrite in 20 parts water. This mixture is allowed to run into a solution containing 10.8 parts 6-hydroxy-naphthostyrile, 2.4 parts sodium hydroxide and 10 parts sodium carbonate in 100 parts of water, the reaction mixture is stirred at 510 for 5 hours, the dyestuff is filtered off with suction, washed with water and dried at 90.

11.3 grams of the dyestulf thus prepared are heated in 100 parts formamide with 4.0 parts crystalline cobalt sulphate and 10 parts sodium acetate at 90 for 4 hours,

is subsequently added with Water and dried at 90.

ness to light and washing.

until the cobalting is completed. The reaction mixture to 500 parts of a 2.5% sodium chloride solution at allowed to cool down, the cobalt complex of the dyestufI is filtered off with suction, washed The cobalt complex dyestufi so obtained dyes superpolyamide fibres in brown-violet shades of very good fast- With the diazo and coupling components listed in the following Table 3 there are obtained further dyestuifs which are converted into their 2:1 cobalt complexes in a manner analogous to that described in Example 78. The cobalt complexes dye superpolyamide fibres from a dispersion in the shades stated in the table:

4-chloro-5-nitro-2-a1ninophenol. 4-chloro6-nitro-2aminophenol. 6-chloro-4-nitro-2-amin0phenol. 2amino-4-hydroxytoluene- 2-aminophenol-4-sulphonic acid dimethylamide 2-aminopl1eu0l-5sulphonic acid dim ethylamide. 1 14. 3-amin0-4-hydroxyphenyl1eth ylsulphone 115 3-amino4-hydroxydiphenylsulphon e -do TAB LE 3 Example Shade 011 Number Diazo component Coupling component polyamide fibres 7e 2-aminophenol fi-hydroxy-naphthostyrile Bordeaux. 80... 4-ehloro-2-aminopheuol do Currant. 81. 4,6-dichloro-Z-aminophenol .do. o. 82 4-nitro-2aminophcnol ..d0. Red-violet. 83. 5-nitro-2-aminophenol "do. Olive. 84 4-chloro-5-nilro-2-aminopheno1. .d0. Olivebrown. 85. 4chlo1'o-6-nitro2-aminophenol.. .do Brownish olive. 86 6-chloro4-nitro-2-aminophenol. ....d0. Olive. 87. 3-amino-4-hydroxytoluene .d0. Yellowish olive. 88- Z-aminopheuol-4-sulphonie acid dnnethylamide ..do Brown-violet. 89 3-amino4-hydroxy-diphenylsulphone Red-violet. 90 Zaminophenol Bordeaux. 91 4-chloro-2-aminophcnol .-d Currant 4,6-dichloro-2-aminophenol- ..d0. Do. 4nitro-2-aminophenol ..d0. Dark brown. 5-nitro-2-aminophen0l "do. Greenlsh grey. 4-chloro-5-nitro-2-aminophenoL ..d0 Olive-brown. i-chloro-fi-nitro-2-amin0pheu0 ..do. Brownlsh olive. 6-ehloro-4-nitro-2-aminopheuo ..do. Olive. 3-amino4-hydroxytoluene -do Yellowisli olive. Z-aminophenolA-sulphonic acid de Brown-violet. 2-aminophenol-5-sulphonic acid dimethylamide Reddish brown. 3-amino4-hyd1'oxyphenyl1-ethylsulphone do Red-violet brown. 3-aminoi-hydroxydiphenylsulphone ..d0 Brown-vlolet. 2-aminophenol Bordeaux. 4-chloro-2eminophen0l Currant. 4,6-dichloro-2-aminophenol D0. 4-nitro-2-aminophenol.... Dark brown. 5-nitro-2-aminophenol Greenish grey.

Olive-brown. Brownish olive. Olive.

: Yellowish olive.

Brown-violet.

. Reddish brown.

Brown-violet.

1 1 Example 116 9.8 parts Z-amino-S-nitro-anisole are dissolved in 100 parts water and 20 parts concentrated hydrochloric acid and the solution is diazotised at with a solution of 4 parts sodium nitrite in 20 parts water. This mixture is added to a solution containing 12.4 parts 1-N-ethyl-6- hydroxy-naphthostyrile, 2.4 parts sodium hydroxide and 10 parts sodium carbonate in 100 parts Water, the reaction mixture is stirred at 10 for 5 hours, the dyestutf is filtered off with suction, thoroughly washed with water and dried at 90.

20 grams of the dyestuif so obtained are dissolved in 250 parts ethylene glycol, a solution of 13 g. crystalline copper sulphate in 125 parts of aqueous ammonia is added, and this mixture is stirred at 100 for 8 hours. The mixture is allowed to cool down, poured into 1000 parts water, the copper complex formed is filtered 011 with suction and washed with a little water.

The dyestuif is decoppered, while still moist, by briefly heating it with 100 parts Water and 100 parts concentrated hydrochloric acid, isolated by filtration after cooling, thoroughly washed with water and dried at 90.

The dyestuff thus prepared is identical with the o,o'-dihydroxy-azo dyestutf which is the basis of Examples 69 and 107 and can be converted by the methods described in Examples 39 and 78 into the 2:1 chromium complex (Example 69) and 2:1 cobalt complex (Example 107), respectively.

Most of the o,o-dihydroxy-azo dyestufis mentioned in Examples 1 to 115 can be prepared in an analogous manner from the corresponding o-hydroxy-o-methoxy-azo dyestuffs.

Example 117 5.7 parts 2-chloroaniline-5-sulphonic acid are dissolved in 50 parts water and 10 parts concentrated hydrochloric acid and the solution is diazotised at 0 with 2 parts sodium nitrite in 10 parts water. This mixture is added to a solution containing 5.4 parts 6-hydroxy-naphthostyrile, 1.2 parts sodium hydroxide and 5 parts sodium carbonate in 50 parts water. The reaction mixture is stirred at 5-15 for 6 hours, the dyestulf is precipitated by the addition of sodium chloride, filtered off with suction and dried at 90.

10 parts of the dyestufl? so obtained are dissolved hot in 400 parts Water and 20 parts of a 35% sodium hydroxide solution and 20 parts of a 25% ammonia solution are added. A solution of 7 parts crystalline copper sulphate in 50 parts 25% ammonia are added at 80 within minutes. The mixture is kept at 80 for 1 hour, the excess sodium hydroxide solution is buffered with hydrochloric acid, the mixture is allowed to cool down, the dyestufi is precipitated by the addition of sodium chloride and filtered off with suction.

By briefly boiling with 100 parts semi-concentrated hydrochloric acid, the copper complex is converted into the free o,o'-dihydr0xy-azo dyestuff. The latter is identical With the dyestuff prepared according to Example 1 from 2-aminophenol-4-sulphonic acid and 6-hydroxy-naphthosty-rile.

A substantial part of the o,o-dihydroxy-azo dyestuffs mentioned in Examples 1-115 can be prepared in a similar manner from the corresponding o-hydroxy-o-chloroazo dyestufis.

Example 118 3.8 parts 3-chloroaniline are dissolved in 50 parts water and 10 parts concentrated hydrochloric acid and the solution is diazotised at 0 with 2 parts sodium nitrite in 10 parts water. This mixture is added to a solution containing 6.2 parts 1-N-ethyl-6-hydroxy-naphthostyrile, 1.2 parts sodium hydroxide and 5 parts sodium carbonate in 50 parts water. The reaction mixture is stirred for 5 hours at 510, the dyestutt" is filtered oif with suction, washed with water and dried at 90.

9 parts of the monoazo dyestuff so obtained are dissolved in 100 parts ethylene glycol, and a solution is added, which contains 7.4 parts crystalline copper sulphate and 8 parts sodium acetate in 200 parts water. The mixture is heated to 60 and 11.4 parts of a 20% hydrogen peroxide solution are added dropwise Within 60 minutes. The mixture is subsequently diluted with 600 parts water, the dyestuff is filtered on with suction and thoroughly washed with water.

The dyestuif is briefly boiled with 100 parts semi-concentrated hydrochloric acid, while still moist, filtered off with suction after cooling, washed and dried. The product is identical with the o,o-dihydroxy-azo dyestuff obtained according to Example 2 from 4-chloro-2-aminophenol and 1-N-ethyl-6-hydroxy-naphthostyrile and can be converted into the 2:1 chromium and cobalt complexes.

A substantial part of the o,o'-dihydroxy-azo dyestuff mentioned in Examples 1-ll5 can be prepared in an analogous manner from the corresponding o-hydroxy-azo dyestufis.

Example 119 5 parts Z-amino-benzthiazole are dissolved in 30 parts concentrated phosphoric acid and the solution is diazotised at 5 with 9 parts nitrosyl-sulphuric acid. The mixture is stirred at -5 for 2 hours and a solution of 7 parts 1-N-n-butyl-6-hydroxy-naphthostyrile in 40 parts glacial acetic acid is subsequently added dropwise below 0. The mixture is stirred for 1 hour, then poured onto 200 parts ice, bufiered with a sodium carbonate solution, the dyestuff is filtered oif with suction and dried at The dyestutf so obtained dyes nickel-modified polypropylene in bluish grey shades of good fastness properties.

Example 120 10 parts of the 2:1 chromium complex dyestuff according to Example 39 are ground with 10 parts of a naphthalene-formaldehyde condensation product and stirred into 10 litres water of pH 6. 10 parts of a levelling adjuvant, e.g. an alkyl-phenyl polyglycol ether, are subsequently added. 1000 parts of a fabric made from synthetic polyamide fibres is introduced into this dyebath and the temperature is slowly raised to After dyeing at this temperature for 1 hour, the material is rinsed, washed and dried. A grey dyeing of very good fastness to light and wet processing is obtained.

Example 121 10 part-s of a dyestufi' according to Example 1 are dissolved in 10 litres water at 40-45", and 10 parts sodium sulphate and 5 parts 30% acetic acid are added. 1000 parts of a woollen fabric are introduced into this dyebath and the temperature is raised to boiling point. Dyeing is carried out at boiling temperature for one hour, 20 parts 50% sulphuric acid are added and boiling is continued for 30 to 45 minutes until the dyebath is exhausted. 100 parts of a 5% potassium dichromate solution are subsequently added to the dyebath which is again boiled for 45 minutes whereby the initially red shade turns olive. After rinsing, Washing and drying, an olive dyeing of very good fastness to light and washing is obtained.

Example 122 14.2 parts of 2-aminophenol-4-sulphonamide are dissolved in 100 parts of water and 25 parts of concentrated hydrochloric acid and diazotised at 0 with a solution of 5 parts of sodium nitrite in 20 parts of water. The diazonium salt solution is added at 0 to a solution of 13.6 parts of 6-hydroxynaphthostyrile, 3 parts of sodium hydroxide and 20 parts of 25 aqueous ammonia solution in 200 parts of water. The mixture is stirred at 5 to 20 for about 5 hours and subsequently 60 parts of sodium chloride added and the dyestuif filtered with suction. The filter residue is slurried in water, rendered acidic by means of hydrochloric acid at 60 to 80, again filtered with 13 suction, thoroughly washed with water and finally dried at 80 to 90.

14 parts of the dyestufi thus obtained are heated at 110 in 100 parts of formami de with 3.9 parts of chro- The o,o-dihydroxy azo dyestuffs which can :be obtained from the diazo and coupling components listed in Table can be transformed into their cobalt complex compounds in analogous manner. They dye wool in the shades listed mium-(III)-chloride-hexahydrate and 8 parts of sodium 5 below:

TABLE 5 Example Diazo Coupling Shade on Number component; component Wool 135 2-aminophenol-4-N-methylsulphouamlde 6-hydr0xy-naphthostyrile Reddish brown. 136 Z-aminophenol-5-sulphonamide d0 Grey-brown.

137 2-aminophenol-5-N-methylsulphouamide .do Do.

I-N-methyl-fi-hydroxy-naphthostyrile Reddish brown.

Grey-brown.

o. Reddish brown.

S OINHI HN- =0 it dyes wool dark brown shades fast to light and to washing.

If using in this example the diazo and coupling components which are listed in the following table monoazo dyestufis are obtainable which are transformed into the 1:2-chromium complex compounds by the method given in this example. The chromium complex dyestulfs dye wool in the shades given in the following table:

Example 146 4.95 parts of the o,o'-dihydroxy azo dyestuff obtained from 4-chloro-2-aminophenol and 6-hydroXy-naphthostyrile in accordance with Example 39 are heated at 160 in 100 parts of ethylene glykol together with 4 parts of chromium-(III)-chloride-hexahydrate for 4 hours. After cooling to 110 4.4 parts of the dyestutf of the formula 8 parts of sodium acetate and parts of formamide are TABLE 4 Example Diazo Coupling shad on Number component component 1 123 2-aminophenol-t-N-methylsulpphonamide fi-hydroxy-napthostyrile B1q,0l:{-b1'Qwn 124 2-aminophenol-5-sulphonamide (10-. oli i h grey. 125 2-aminophenol-5-N-methylsulphonamrde 126 Z-aminophenol-4-sulphouarnide -methy ydroxy-naphthostyrlle Black-brown. 127 2-aminophenol-4-N-methylsulph0uam Do. 128 2-arninophenol-5-sulphonamide do.. Grey-ollve. 129 2-an1inophenol-5-N-methylsulphonam1de r .do D o. 130 Z-aminopheuolt-sulphonamide 1-N-ethyl-G-hydroxy-naphthostynle- Black-b n, 131 2-aminophenol--N-methylsulphouamide ..do Do. 132 2-aminophenol-fi-sulphonamide -do Grey-ohve, 133 2-aminophenol-5-N-methylsulphonamide d0 Do.

Example 134 14 parts of the o,o-dihydroxy azo dyestutf obtained from diazotised 2-aminophenol-4-sulphonamide and 6- hydroxynaphthostyrile in accordance with the method given in Example 122 are heated to 90 in 100 parts of formamide together with 4.1 parts of crystalline cob-alt sulphate and 5 parts of sodium acetate for 4 hours. The mixture is then stirred into 500 parts of 10% sodium chloride solution at 80, kept at this temperature for one hour and then filtered with suction, washed with sodium chloride solution and dried at 90.

The 1:2-ooba1t complex dyestutf thus obtained dye's wool reddish brown shades of good fastness to light and washing.

added and the mixture stirred for 2 hours at 110". Then it is added to a solution of 500 parts of 2% sodium chloride at stirred at this temperature for one hour, filtered with suction, thoroughly washed with water and dried at 80.

The mixed chromium complex obtained yields on polyamide fibres a black-currant dyeing of very good fastness to light and washing.

Most of the dyestuffs named in Tables 1, 2 and 4 can be transformed into the mixed chromium complexes when metal-complexed an analogous manner in the presence of a second o,o'-dihydroxy azo dyestutf. Table 6 shows the dye-shades of some mixed complex dyestuffs in polyamide fibrels. Table 7 shows the shades of some dyestuffs on woo TABLE 6 Example Sh 1 Number 1. Component 2. Component am i g 12 1135 y 147 ([JH 11(1) (311 H? Navy blue.

02N N=N N= 01 EN O C1 148 Same as Ex. No. 147 above. (|)H H Brownish black.

ONENQ 149 Same as Ex. No. 147 above. (IJH HC| Black currant.

E T =N-:

150 Same as Ex. N0. 147 above. OH E0 I Greenish black.

151 Same as Ex. No. 147 above. (])H H? Blue-grey.

C1 HN=N 152 Same as Ex. No. 147 above; (|)H HC') Do.

153 Same as Ex. No. 147 above. Oli-I HCI) Currant.

N Oz

154 Same as Ex. No. 147 above. 7 0H Do.

N OzN EN :0

155 Same as Ex. No. 147 above. ?H Red violetbrown.

N=N TIT-CH TABLE 6Continued Example Shade on poly- N umber 1. Component 2. Component amide fibre 156 Same as Ex. No. 147 above. (|)H Dark brown.

N=N WCH: OzN lN H O l 157 OH HO OH Blue-black.

| NO: HO I N20 EN 0 158 Same as Ex. No. 157 above. (IJH H(|) Grey.

159 Same as Ex. No. 157 above. (1)11 HCI) Black-olive.

160 Same as Ex. No. 157 above. C| H Dark-brown;

N=N "CH (:1 I N HO I 161 Same as Ex. No. 157 above. ()H Do.

N=N1] m OH:

NO: N

H O l 162 (5)11 Ht) ()H H? Olive black.

N 02 C2H5N-O 163 Same as Ex. N0. 162 above. OH HO Black.

TABLE 6Continued Example Shade on poly- Number 1. Component 2. Component amide fibre 164 Same as Ex. N o. 162 above. Red-brown.

N=N TIE-CH3 165 Same as Ex. N o. 162 above. D0.

166 (|)H H? I H H? BIack-eurmnt.

01 /CH3 SOzN HN 0 167 Same as Ex. N0. 166 above. l H(|) 13 i h bl 168 Same as Ex. No. 166 above. I Brown.

01 1N 11 O 169 Same as Ex. No. 166 above.

TABLE 7 Example Number 1. Component 2. Component Shade on wool 170 $11 H0 ()H H(|) Grey.

N=N N=N S OzNHg TABLE 7-Cont1nued Example Number 1. Component 2. Component Shade on wool 171 Same as Ex. N0. 170 above. (|)H Brown.

-N=N -1'|CH; SOzNH2 172 r. (|)H H? C| H H? Brownlsh grey.

SOzNHz N0; EN ---0 173 Same as Ex. No. 172 above. OH Dark brown.

I l L SOzNHz 174 (|)H H(|) (|)H Brown. N=N N=N--l uTor-n SO NH HO I SO2NH2 HN 0 175 Same as Ex. No. 174 above. (HI EC) Black.

SO2NH2 We claim: convertible into a metal complex by mctallization in the 1. A metal dyestuif complex of 1 mole of a metal selected from the group consisting of chromium, cobalt, copper, iron, and nickel; and 2 moles of compounds having the formula wherein A is selected from the group consisting of phenylene; phenylene substituted with chloro, nitro, acetylamino, sulfonic acid, sulfonamide, alkyl sulfonarnide having 1 to 2 carbon atoms in the alkyl group, hydroxyethyl sulfonamide, sulfonic acid morpholide, alkyl having 1 to 2 carbon atoms, carboxyl, alkyl, sulfonyl having 1 to 2 carbon atoms, phenyl sulfonyl or OCH SO naphthylene, naphthylene substituted with nitro, carboxyl, or sulfonic acid; 'benzothiazole; and alkoxy benzothiazole having 1 to 2 carbon atoms in the alkoxy group; X is a substituent in the position adjacent to the azo bridge in the A-radical, and is a metal-complex forming group or a substituent presence of an oxidizing agent and is selected from the group consisting of hydroxyl, carboxyl, methoxy, sulfo, and hydrogen; R is hydrogen, an alkyl group having 1 to 6 carbon atoms, a fl-hydroxyethyl group, a fl-chloroethyl group, a fi-cyanoethyl group, a fi-acetoxyethyl group, a. fi-carbethoxy group, or a p-carboxyethyl group; R is hydrogen, chlorine, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms in the alkyl radical, acetylamino, sulfonylamino, nitro, sulfonic acid, carboxylic acid, or sulphonamide; and n is the integer 1 or 2.

2. A dyestufi of claim 1 corresponding to the formula (C O)mOH HO R: l

wherein m stands for the number 0 or 1, R stands for hydrogen, chlorine, bromine, nitro or sulfonamide, R stands for hydrogen, chlorine or sulfonic acid group, R stands for hydrogen, methyl or ethyl; and the chromium or cobalt complex compounds of said dyestuff.

3. A dyestuif of claim 1 corresponding to the formula -or ,o

RNC=O wherein R stands for hydrogen, chlorine, bromine, nitro or sulfonamide, R stands for hydrogen, chlorine or sulfonic acid group, and R stands for hydrogen, methyl or ethyl.

4. A dyestuif of claim 1 corresponding to the formula s I Y HN-C=O 6. The 1:2 molar complex of chromium and the dyestuff of claim 1 corresponding to the formula 7. The 1:2 molar complex of chromium and the dyestuif of claim 1 corresponding to the formula 8. The 1:2 molar complex of cobalt and the dyestufi of claim 1 corresponding to the formula 9. The 1:2 molar complex of chromium and the dyestufl of claim 1 corresponding to the formula 10. The 1:2 molar complex of chromium and the dyestuff of claim 1 corresponding to the formula 11. The 1:2 molar complex of chromium of the dyestulf of claim 1 corresponding to the formula N-C=O 12. The 1:2 molar complex of chromium of the dyestuff of claim 1 corresponding to the formula Hie-a0 13. The 1:2 molar complex of chromium of the dyestuif of claim 1 corresponding to the formula 14. The 1:2 molar complex of chromium and the dyestuff of claim 1 corresponding to the formula HN-C=O 15. A metal dyestuif complex of 1 mole of a metal selected from the group consisting of chromium, cobalt, copper, iron, and nickel; and 2 moles of dyestuffs having the formula H o X lI-N=N- \2*( Rah I :0

R1N the second of said dyestuffs being a monoazo dyestuiT having a metal complex forming group X is the o and 0' positions to the azo groups; wherein A is selected from the group consisting of phenylene; phenylene substituted with chloro, nitro, acetylamino, sulfonic acid, sulfonamide, alkyl sulfonamide having 1 to 2 carbon atoms in the alkyl group; hydroxyethyl sulfonamide, sulfonic acid morpholide, alkyl having 1 to 2 carbon atoms, carboxyl, alkyl sulfonyl having 1 to 2 carbon atoms, phenyl sulfonyl or OCH SO naphthylene; naphthylene substituted with nitro, carboxyl, tor sulfonic acid; benzothiazole; and alkoxy benzothiazole having 1 to 2 carbon atoms in the alkoxy group; X is a substituent in the position adjacent to the azo bridge in the A-radical, and is a metal-complex forming group or a substituent convertible into a metal complex by rnetallization in the presence of an oxidizing agent and is selected from the group consisting of hydroxyl, carboxyl, methoxy, sulfo, and hydrogen; R is hydrogen, an alkyl group having 0 to 6 carbon atoms, a fl-hydroxyethyl group, a fl-chloroethyl group, a fi-cyanoethyl group, a B-acetoxyethyl group, a fi-carbethoxyethyl group, or a fl-carboxyethyl group; R is hydrogen, ch10- rine, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms in the alkyl radical, acetylamino, sulfonylamino, nitro, sulfonic acid, carboxylic acid, or sulphonamide; and n is the integer 1 or 2.

References Cited UNITED STATES PATENTS 26 Zerweck et a1 260326.5 Brody et a1. 260152 XR Dorlars et a1. 260-146 Kuster 260-146 Enders et a1. 260146 Fuchs et a1. 260152 Du Peloux et a1. 260-152 XR Roue et a1. 260-146 XR FOREIGN PATENTS U.S. Cl. X.R. 

